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Potential energy surfaces

Potential energy surfaces

Chapter:

(p.35)
3 Potential energy surfaces

Source:

Theories of Molecular Reaction Dynamics

Author(s):

Niels E. Henriksen

Flemming Y. Hansen

Publisher:

Oxford University Press

DOI:10.1093/acprof:oso/9780199203864.003.0003

This chapter discusses potential energy surfaces, that is, the electronic energy as a function of the internuclear coordinates as obtained from the electronic Schrödinger equation. It focuses on the general topology of such energy surfaces for unimolecular and bimolecular reactions. To that end, concepts like saddle point, barrier height, minimum-energy path, and early and late barriers are discussed. It concludes with a discussion of approximate analytical solutions to the electronic Schrödinger equation, in particular, the interaction of three hydrogen atoms expressed in terms of Coulomb and exchange integrals, as described by the so-called London equation. From this equation it is concluded that the total electronic energy is not equal to the sum of H-H pair energies. Finally, a semi-empirical extension of the London equation — the LEPS method — allows for a simple but somewhat crude construction of potential energy surfaces.

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PRINTED FROM OXFORD SCHOLARSHIP ONLINE (www.oxfordscholarship.com). (c) Copyright Oxford University Press, 2018. All Rights Reserved. Under the terms of the licence agreement, an individual user may print out a PDF of a single chapter of a monograph in OSO for personal use (for details see www.oxfordscholarship.com/page/privacy-policy).date: 19 November 2018